Formamidine compounds containing trihalomethyl groups

ABSTRACT

A composition of matter is described herein which has insecticidal and miticidal activity and methods of use. The composition may be defined by the following generic formula:   WHEREIN R1 and R2 are independently methyl or halogen, preferably methyl or chlorine; R3 is selected from the group of CF3, -CF2Cl, -CFCl2 and -CCl3; and R4 is selected from the group of -H, -CF3, -CF2Cl, -CFCl2 and -CCl3.

United States Patent [191 Pallos [4 Jan. 21, 1975 FORMAMIDINE COMPOUNDS CONTAINING TRIHALOMETHYL GROUPS [21] Appl. No.: 449,793

[52] US. Cl. 260/564 RF, 424/326 [51] Int. Cl. C07c 123/00 [58] Field of Search 260/564 RF [56] References Cited UNITED STATES PATENTS 3,557,128 l/l97l Pallos et al. 260/564 RF Primary Examiner-Bernard Helfm Assistant Examiner-Gerald A. Schwartz Attorney, Agent, or Firm-Michael J. Bradley [57] ABSTRACT A composition of matter is described herein which has insecticidal and miticidal activity and methods of use. The composition may be defined by the following generic formula:

wherein R and R are independently methyl or halogen, preferably methyl or chlorine; R is selected from the group of CF,, CF Cl, -CFCl and CCl and R is selected from the group of H, C F CF Cl, CFCl and CCl 13 Claims, N0 Drawings FORMAMIDINE COMPOUNDS CONTAINING TRIHALOMETHYL GROUPS BACKGROUND OF THE INVENTION Among the many insecticidal and miticidal com- BRIEF DESCRIPTION OF THE INVENTION It has been discovered that certain substituted formamidine compounds are useful as insecticidal and miticidal compounds. These substituted formamidine compounds may be defined by the following generic formula:

CH R

wherein R and R are independently methyl or halogen, preferably methyl or chlorine; R is selected from the group of -CF CF Cl, CFCl and -CCl and R is selected from the group of H, CF CF Cl, CFC1 and -CCl DETAILED DESCRIPTION OF THE INVENTION In the practice of the present invention, the compounds of the present invention are manufactured by reacting the properly selected 2,4 disubstituted aniline with an alkyl orthoformate and then reacting the resulting alkylformamidate with methyl amine to obtain the l-methyl-3-disubstituted phenyl formamidine which in turn is reacted with a halogenated aldehyde or ketone to produce the desired formamidine addition product as shown in the examples herein.

After the compounds of the present invention are formed, they can be applied to the habitat in an effective amount to control mites and insects.

The following examples illustrate the merits of the present invention:

EXAMPLE I l-Methyl-l-[a,a-bis(dif'luorochloromethyl)] hydroxymethyl-3-(2-methyl-4'-chlorophenyl) formamidine Into a round-bottom flask fitted with a stirrer, was placed 1.8 g (0.01 mole) 1-Methyl-3-(2-methyl-4'- chlorophenyl) formamidine dissolved in ml CH Cl 2.0 g (0.01 mole) Symtetrafluorodichloroacetone dissolved in 5 ml CH CI were added dropwise to the flask producing a slightly isothermic reaction. The reaction mixture was stirred at room temperature for two hours and evaporated. The reaction yielded 3.2 g of a solid product melting at l07-1 10C. Structure confirmation was by N.M.R.

Other compounds can be prepared in an analogous manner starting with the appropriate materials as outlined above. Following is a table of compounds representative of those embodied in the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of this specification.

TABLE I 3 3 R G N=CH-N-( 3-0H Compound Number R R; 4

I Cl CH CF Cl CFgCl 2 Cl CH CF CI CFCl Insecticidal activity of the above compounds were evaluated for efficacy on various insect species as follows:

I. Salt-marsh Caterpillar [Estigmene acrea (Drury)] A. Leaf Dip Assay to Determine Efficacy Against First Instar Salt-marsh Caterpillar Larvae Kidney Bean leaves are dipped in a 50-50 acetonewater solution of the test chemical. When the leaves have dried, egg masses of the Salt-marsh Caterpillars are placed on the leaf surface. Mortality of the newly hatched larvae is determined after one week. Test concentrations range from 0.05 percent down to that at which approximately 50 percent of the larvae are dead.

B. Ovicidal Screening Procedure Egg masses of the Salt-marsh Caterpillar are dipped in acetone solutions of the test chemicals and placed in petri dishes containing a portion of larval rearing medium. Efficacy is determined after seven days by observing the number of newly emerged larvae. Test concentrations range from 0.05 percent down to that at which approximately 50 percent of the eggs do not hatch.

II. Black Bean Aphid [Aphis fabae (Scop.)]

Nasturtium (Tropaeolum sp.) plants, approximately 23 inches tall, are transplanted into sandy loam soil in 3-inch clay pots and infested with 50-75 aphids of mixed ages. Twenty-four hours later they are sprayed, to the point of runoff, with aqueous suspensions of the toxicant. The suspensions are prepared by diluting aliquots of the toxicant, dissolved in an appropriate solvent, with water to which has been added 0.0002 percent of a conventional wetting agent such as polyoxy-ethylene sorbitan monolaurate ether of alkylated phenol blended with organic sulfonate. Test concentrations ranged from 0.05 percent to that at which 50 percent mortality is obtained. Mortality is recorded after 48 hours and the LD-50 valves are expressed as percent active ingredient in the aqueous suspensions.

III. Two-spotted Mite [Tetranychus urticae (Koch)] Pinto Beans (Phaseolus sp.) plants, approximately 2-3 inches tall, are transplanted into sandy loam soil in 3-inch clay pots and infested with 5075 mites of mixed ages. Twenty-four hours later they are sprayed, to the point of runoff, with aqueous suspensions of the toxicant. The suspensions are prepared as in previously described tests (I and II). Test concentrations ranged from 0.05 percent to that at which 50 percent mortality is obtained. Mortality of adults, nymphs and eggs is recorded after 7 days and the LD-SO values are expressed as percent active ingredient in the aqueous suspensrons.

IV. Systemic Tests A. Salt-marsh Caterpillar:

Aliquots of toxicant dissolved in an appropriate solvent are diluted in water and placed in glass bottles. Concentrations of active ingredient range from 10 ppm to that at which 50% mortality is obtained. Kidney Beans (Phaseolus vulgaris), supported by cotton plugs, are inserted into the solution so that the roots and major portion of the stem are completely immersed. Masses of caterpillar eggs which are nearly ready to hatch are fastened to the bean leaves. One week later mortality of the newly hatched larvae is recorded. LD-SO values are expressed as ppm of toxicant in the aqueous suspensions.

B. Two-spotted Mite:

Preparation of the test solution and concentrations is the same as for the Salt-marsh Caterpillar test (IV-A). Pinto Bean (Phaseolus sp.) plants with expanded primary leaves are placed in the solution so that the roots and major portions of the stem are completely immersed. Immediately after, the leaves are infested with 75-100 mites of various ages. Mortality of adults, nymphs and eggs is recorded after one week, and LD-SO values are expressed as ppm of toxicant in the active compounds can be applied directly to feedstuffs, seeds, etc. upon which these pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. ln connection with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served to the compound as rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pests.

The precise manner in which the pesticidal compositions of this invention are used in any particular instance, will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid composition. For example, an emulsion, suspension or aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 15.0 percent by weight of the pesticidal composition. Preferably, however, the pesticidal compositions of this invention will be in the form of solutions or suspensions containing from about 0.1 to about 1.0 percent by weight of the active pesticide compound.

What is claimed is:

1. The compounds having the formula:

aqueous suspensions. f 3/ 3 The results of the above test procedures indicate in R Table 11 the effective concentration at which LD-SO l I control effect was achieved on the various species of R 4 insects. 2

TABLE 11 SMC 2SM Compound BA Leaf Ovicide SYS Pe Eggs SYS Number 7! Dip ppm 7r 7! ppm 1 .008 .0003 .03 .08 .01 .05 10 2 .03 .00008 .03 .08 .03 05 10 SMC Salt-marsh Caterpillar SYS Systemic 25M Two-spotted Mite BA Bean Aphid greater than less than Pe Post-embryonic The compounds of this invention are generally embodied into a form suitable for convenient application. For example, the compounds can be embodied into pesticidal compositions which are provided in the form of emulsion, suspensions, solutions, dust and aerosol sprays. In general, such compositions will contain, in addition to the active compound, the adjuvants which are normally found in pesticide preparations. ln these compositions, the active compounds of this invention can be employed as a sole pesticide component or they can be used in a mixture with other compounds having similar utility. The pesticide compositions of this invention can contain as adjuvants organic solvents such as sesame oil; xylene solvents; heavy petroleum, etc; water; emulsifying agents; surface active agents; talc, pyrophyllite; diatomite; gypsum; clays; propellents; such as dichlorodifluormethane, etc. If desired, however, the

wherein R, and R are independently methyl or halogen; R is selected from the group of CF;,, CF Cl, CFC1 and CCl and R, is selected from the group of H, CF CF Cl, CFCl and CCl;,.

2. A compound as set forth in claim 1 wherein R, and R are independently methyl or chlorine; R is selected from the group of CF CF Cl, CFCl, and CCl and R is selected from the group of H, CF CF Cl, -CFC1 and CCl;,.

3. A compound as set forth in claim 1 wherein R, is Cl; R is CH,,; R is CFgCl and R, is CF Cl.

4. A compound as set forth in claim 1 wherein R, is Cl; R is CH;,; R is -CF Cl and R, is CFCl 5. A compound as set forth in claim I wherein R, is Cl; R is --CH;,; R is CF, and R, is CF,,.

6. A compound as set forth in claim 1 wherein R, is Cl; R is CH;,; R is CF, and R is CF Cl.

7. A compound as set forth in claim 1 wherein R is Cl; R is CH R is -CFCl and R is -CFCl 8. A compound as set forth in claim 1 wherein R is --Cl; R is --CH:,; R is CFCl and R is --CCl 9. A compound as set forth in claim 1 wherein R is -Cl; R is CH R is CCl and R is CCI 10. A compound as set forth in claim 1 wherein R iS R2 iS R3 is and R4 iS 

2. A compound as set forth in claim 1 wherein R1 and R2 are independently methyl or chlorine; R3 is selected from the group of -CF3, -CF2Cl, -CFCl2 and -CCl3; and R4 is selected from the group of -H, -CF3, -CF2Cl, -CFCl2 and -CCl3.
 3. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CF2Cl and R4 is -CF2Cl.
 4. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CF2Cl and R4 is -CFCl2.
 5. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CF3 and R4 is -CF3.
 6. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CF3 and R4 is -CF2Cl.
 7. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CFCl2 and R4 is -CFCl2.
 8. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CFCl2 and R4 is -CCl3.
 9. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CCl3 and R4 is -CCl3.
 10. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CCl3 and R4 is -H.
 11. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CF3 and R4 is -H.
 12. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CF2Cl and R4 is -H.
 13. A compound as set forth in claim 1 wherein R1 is -Cl; R2 is -CH3; R3 is -CFCl2 and R4 is -H. 